Glycidyl ethers



United States Patent 3,244,731 GLYCIDYL ETHERS Graham Winfield, Harlton,Camhridgeshire, and Edward William Garnish, Saffron Walden, Essex,England, assignors to Ciba Limited, Basel, Switzerland, a company ofSwitzerland No Drawing. Filed Apr. 19, 1962, fier. No. 186,315 Claimspriority, application Great Britain, Apr. 13, 1961, 13,401/ 61; June 9,1961, 21,023/61 14 Claims. (Cl. Z60348) A o BI I(IJHCIJH-OCHQC OHR L R1R: (I) wherein B represents a substituted or unsubstituted, mono nuclearor polynuclear aromatic residue with X valencies, A represents analiphatic, cycloaliphatic, araiiphatic or aromatic hydrocarbon residueor a grouping of the formula:

I I CHCH-O CHzCH--CHR and where R and R when taken separately representhydrogen atoms or saturated or unsaturated aliphatic, aromatic oraraliphatic hydrocarbon residues or when taken together represents achain of three or four methylene groups and R represents a hydrogen atomor a methyl group, and X is an integer of at least 1.

The epoxide compounds of general Formula I are transparent and liquid atroom temperature or readily fusible and may be readily reacted, eitheralone or in admixture with the commonly known epoxy resins, with theusual hardening agents employed for the known epoxy resins, such asdicarboxylic anhydrides, amines, polyphenols and Lewis acids. Aparticular advantage associated with the compounds of the generalFormula I is that, when used either alone or in admixture with thecommonly known epoxide resins, they give a very rapid cure whenanhydrides, and/ or polyphenolic curing agents are employed.

The new materials therefore find use both as rapidly hardenable resinsand as accelerators in systems containing a commonly known epoxide resintogether with an anhydride and/ or polyphenolic curing agent. In thislatter capacity they have a decided advantage over the currently usedtertiary amines such as benzyldimethylamine in that they form stable,storable mixtures with known epoxide resins and consequently the resinand curing agent can be supplied as a two component system. When atertiary amine such as benzyldimethylamine is used as an accelerator itcannot be supplied in admixture with the resin because such a mixturewill gel on storage, and therefore a three component system isnecessary.

One preferred group of epoxide compounds according to the presentinvention is constituted by the mononuclear compounds of the generalFormula II.

in which R R and R have the meanings assigned to them above, Zrepresents a monovalent aliphatic, cycloah- 3,244,731 Patented Apr. 5,1966 phatic, araliphatic or aromatic hydrocarbon residue and X X eachrepresents hydrogen atoms or halogen atoms, alkoxy groups nitro groupsor aliphatic, cycloaliphatic or araliphatic hydrocarbon groups or two ofthe X together may represent a fused benzene or other aromatic ring.Compounds of the general Formula II contain only one glycidyl ethergrouping and in many cases are particularly valuable as reactivediluents for epoxy resins containing two or more reactive epoxy groups.The simpler members of this class, e.g. those where R and R are hydrogenatoms and those where Z is a lower alkyl group (containing for exampleup to 3 carbon atoms), are mobile liquids and may be used as viscositymodifiers for conventional polyepoxide compositions. Furthermore,compounds of the general Formula II when used in admixture withpolyepoxides serve to control the degree of crosslinking in the curedepoxy resin composition and in addition may be used as components ofpolyesters.

Another preferred group of compounds within the scope of the presentinvention is constituted by compounds of the general Formula III:

i X NCH-([)HOCH2CHCHR3 R1 R2 2 X X (III) X4 in R2 0 X3 n N where n is 1or 2 and X -X R R and R have the meanings assigned to them above.

A further preferred group of compounds according to the presentinvention is constituted by the compounds of general Formula V:

in which ,A, R R and R and n have the meanings given to them above, Yrepresents a divalent radical such as an oxygen or sulfur atom, asulfone ($0 grouping, a carbonyl group or a disubstituted carbon atom ofthe type 4. inorganic salt formed during the reaction is removed byfiltration and/or with water and the excess epihalohydrin and solventremoved by vacuum distillation.

It is to be noted that the production of the glycidyl ethers andsubstituted glycidyl ethers of N-arylethanolamines as just described isessentially similar to the production of glycidyl ethers of phenols. Itdiffers considerably from the method employed for the production ofglycidyl ethers of polyols, which cannot be produced in good yield by aone step method from the epihalohydrin and the polyol in alkali butnecessitate the prior reaction of the epihalohydrin withthe polyol inthe presence of a Lewis acid followed by alkali-catalyzed ring closureto the glycidyl ether. The use of Lewis acids also causes the productionof by-products such as polymers of the epihalohydr'm, and deleteriousproducts containing ionisable halogen, by reaction of epihalohydrin withthe halowhere A, X X' R R and R have the meanings previously assigned,c, 11, represent hydrogen atoms or lower alkyl groups of not more than 4carbon atoms and where q is 1 or a high integer.

According to a further feature of the invention the glycidyl ethers ofthe present invention are produced by the reaction of substancescontaining one or more of the groupings of general Formula VII:

R R (VII) attached to an aromatic nucleus (where R and R have themeanings previously assigned and A represents a monovalent aliphatic,cycloaliphatic, araliphatic or aromatic hydrocarbon residue or is agroup of the general formula:

(where R and R have the meanings previously assigned) withepichlorhydrin, glycerol dichlorohydrin or other halohydrin orepihalohydrin, or with the 3-methyl, analogous such as2,3-epoxybutylchloride in the presence of suitable bases. For theproduction of compounds with a high epoxy value it is preferable toemploy the epichlorohydrin or analogous epihalohydrin or dihalohydrin inexcess of the stoichiometric quantity; use of the stoichiometricquantity or of a deficiency of the epihalohydrin or dihalohydrin givesrise to high molecular weight products formed by further reaction ofalcohols involved with the epoxy groups in the resin, analogous to thoseproduced from polyphenols and epichlorohydrin. Suitable ,bases for thecondensation are sodium hydroxide and potassium hydroxide.

The hydroxide is usually employed in the ratio 1 to 1.5

equivalents per equivalent of hydroxyl group in the N- peratures withinthe range 2 0 to 180 C., but is preferably conducted between 40 C. andthe boiling point of the mixture. Preferably, when the reaction iscomplete, the

q X1 X: (VI) hydrin first formed from the alcoholic groups of the polyoland the epihalohydrin, e.g.:

O OH

The alcohols of general Formula V may also be converted into theirglycidyl ethers using the two step reaction involving Lewis acids butless pure products are formed and the direct alkali-catalysed reactionis preferred.

The N-arylethanolamines of the present invention are readily obtained bycondensation of 1:2-epoxides or the corresponding hailohydrins witharomaticamines and polyamines. Suitable lz2-epoxides for the preparationof the N-arylethanolamines used in the present invention as precursorsof the glycidyl and substituted glycidy1ethers are ethylene oxide,propylene oxide, 1:2-epoxybutane, 2:3epoxybutane, butadiene monoxide,allyl glycidyl ether, cyclohexane oxide, cyclopentane oxide and styreneoxide. The epoxides may be directly reacted with the aromatic amines, orthe corresponding halohydrins, may be employed in the presence of a baseto effect elimination of the haloacid.

Suitable aromatic amines for. the production of the mononuclearN-arylethanolamines which are employed as intermediates for theproduction of glycidyl ethers of general Formula II are:N-methylaniline, N-methyltolui dine, Nethyl-toluidine, N-ethyl, O-ethyland p-ethylaniline, p-chloro-N-methyl aniline, p-chlorotoluidine,pmethoxy-N-methyl-aniline, diphenylamine, N-cyclohexylaniline, N-methylaand fi-naphthylamine.

Suitable aromatic amines for the production of the mononuclear N-arylethanolamines employed as intermediates for the production ofglycidylethers of general Formula III are: N,N-dimethyl 0-, mand p-phenylenediamine, N,N'-diethyl o-, mand p-phenylene diamine,N,N'dimethyl-2,4-diaminotoluene,N-,N'-dimethyl-2,4-diaminochlorobenzene.

Suitable aromatic amines for the production of mononuclear N-arylethanolamines employed as intermediates for the production of glycidylethers of general Formula IV are: aniline, o-, m-, p-toluidine, o-, m-,p-nitro-aniline, 2,4-dinitroaniline, o-, m-, p-anisidine, thechloroanilines,

the bromoanilines, o-, m-, p-phenylene diamine, o-, m-, .p-ethylaniline,aand fi-naphthylamine.

Suitable aromatic amines for the production of dinuclear N-arylethanolamines of general Formula VIII:

I l X" N-OHCHOH iv X3 (VIII) Where A, R R Y, X -X X" -X" and p have themeanings given above, which are converted into the glycidyl ethers ofgeneral Formula V are: benzidine, oand p-toluidine, oand p-dianisidine,diaminodiphenylsulfone, diamino-diphenyl ketone, diaminodiphenylether,diaminodiphenyl sulfide, methylene dianiline,N,Ndimethylmethylenedianiline, methylene ditoluidine, Z-ethyl methylenedianiline and like dinuclear aromatic amines which are normally preparedby the controlled acid-catalysed condensation of mononuclear aromaticamines such as aniline, N-methylaniline and the toluidines withaliphatic aldehydes and ketones such as formaldehyde, acetaldehyde,propionaldehyde, acetone, methyl ethyl ketone, cyclopentanone andcyclohexanone. It is noteworthy that many of the dinuclear N-arylethanolamines may also be obtained by the direct condensation ofmononuclear Naryl ethanolamines with suitable aldehydes and 3 ketones.

Suitable polyamines for the production of the polynuclear N-arylethanolamines of general Formula IX:

phthalic anhydride,

The epoxides of general Formula I react with the following hardeners:amines such as aliphatic and aromatic primary and secondary amines, e.g.mono-, di-, and tributylamine, p-phenylenediamine, bis-(p-aminophenyD- 5methane, ethylenediamine, N:N-diethyl-ethylenediamine,

diethylenetriamine, tetra (hydroxyethyl) diethylenetriamine,triethylene-tetramine, tetraethylenepentamine, diethylamine,triethanolamine, piperidine, guanidine, and guanidine derivatives, suchas phenyl-guanidine and di- 1O phenylguanidine, dicyandiamide,aniline-formaldehyde resins, polymers of aminostyrenes, polyamides, e.g.those from aliphatic polyamines and dior trimerized unsaturated fattyacids, isocyanates, isothiocyanates, polyhydric phenols, e.g.resorcinol, hydroquinone, and bis(4-hydroxy- 15 phenyl)-dimethylmethane,phenol-aldehyde resins, oilanhydride. Mannich bases and Friedel-Craftscatalysts,

e.g. A101 SnCl SnCl BF and their complexes with organic compounds andphosphoric acid will also effect hardening of compounds or" generalFormula I by catalysing their homopolymerization.

According to a further feature of the present invention therefore, thereare provided hardenable compositions which comprise one or more epoxycompounds of general Formula I together with one or more hardeningagents therefore where at least one of the epoxide com- 5 pounds is adiepoxide.

I l I-JlH-CHOH used in the production of polyglycidyl ethers of generalFormula VI, wherein A, c, d, R R q and X' -X' have the meaningspreviously given, are aniline formaldehyde resins, toluidineformaldehyde resins and the polynuclear polyamines of general Formula X:

-wherein c, d, q, and X' X have the meanings previously assigned and Drepresents a hydrogen atom, ora monovalent hydrocarbon substituent suchas an aliphatic,

' cycloaliphatic or aromatic residue, and which are formed pounds inwhich the epoxy group has further reacted with alcohols of generalFormula V and/or other polyhydroxy compounds which promotecross-linking, such as hexanetriol. Other epoxides may also be presentin the compositions of this invention, e.g. monoor polyglycidyl ethersof monoor poly-alcohols, such as butyl alcohol, butane-1:4-diol orglycerine, or of monoor poly-phenols, such as resorcinol,bis-(4-hydroxyphenyl)- dimethyl-methane or condensation products ofaldehydes with phenols (Novolaks), polyglycidyl esters of polycarboxylicacids, such as phthalic acid, or aminopolyepoxides such as are obtainedby dehydrohalogenation of the reaction products from epihalohydrins andprimary or secondary amines such as n-butylamine, aniline or4:4-di(monoinethylamino)-diphenylmethane.

The hardenable compositions may also contain fillers,

plasticisers and coloring agents, for example, asphalt,

bitumen, glass fibers, mica, quartz powder, cellulose, kaolin, finelydivided kieselguhr (Aerosil) or metal powder.

The aforesaid compositions may be used in the filler-or unfilled state,eg in the form of solutions or emulsions,

as textile auxiliaries, laminating resins, varnishes, lacquers, dippingresins, casting resins and encapsulating, coating, filling and packingmaterials, adhesives and the like, as well as for the preparation ofsuch materials. The new resins are especially valuable as insulatingmaterials for the electrical industry.

methyl ethyl ketone (20 ml.).

In the following examples which illustrate the invention, temperature isin Centigrade and parts are by weight. Where heat deflectiontemperatures and flexural strengths are given they were measured inaccordance with the procedures laid down and published by The AmericanSociety for Testing Materials, the reference numbers of the tests beingASTM D648-56 and ASTM D790-59T respectively.

Example 1 N-phenyldiethanolamine (122 g. 0.66 mol) and epichlorohydrin(370 g. 4 mol) were charged into a flask fitted with stirrer, waterentrainer, and reflux condenser. The mixture was heated, to effectsolution of the amine. When the solution had reached 80-90 C. a solutionof 5 g. of sodium hydroxide in 5 ml. of water and 2.5 ml. ofmethoxyethanol was added with stirring. An exothermic reaction set inandthe mixture began to boil. After initial reaction had abated afurther 5 g. of sodium hydroxide, in flake form, was added. Theadditions of alkali were continued over a period of 3 /2 hours until atotal of 72 g. of sodium hydroxide had been added to the flask. Thereaction mixture was held at the boiling point by the exothermicreaction and application of heat for a further hour after the additionshad been completed. During this reaction period water in the distillatewas collected in the entrainer and epichlorohydrin in the distillatereturned to the flask.

The reaction mixture was then allowed to cool slightly, and thenfiltered and the filtrate evaporated to recover :excess epichlorohydrin.The residue was taken up in trichloroethylene, washed with water, andthe product recovered by evaportaion of the solvent. The yield was 168g. (86% of theory) of a liquid amber resin containing 5.24 epoxy eq./kg.and 0.04 chlorohydrin eq./kg. Viscosity at 21 C.:5 poises.

Example 2 Example 3 p 30 parts by weight of the resin of Example 1 weremixed with 70 parts by weight of Resin A referred to.

in Example 2 and 77 parts by Weight of hexahydrophthalic anhydride. Thismixture gelled in .2 hours at 80 C. and after 8 hours at 120 C. hadcured to a hard, tough resin which had a heat deflection temperature of70 C. and a flexural stregnth of 857 kg./sq. cm.

Example 4 N-phenyldiethanolamine (45 g.) and stannic chloride (0.5 ml.)were measured into a flask fitted with stirrer, dropping funnel, andreflux condenser. The stirred mixture was heated to 8085 C.Epichlorohydrin (46 g.) was added at this temperature over a period ofmin. without any detectable exothermic reaction occurring. The internaltemperature was then raised to 140 C. and

held for sixteen hours.

The reaction mixture was cooled and diluted with This solution wasstirred vigorously with aqueous sodium hydroxide g. in ml. water) at C.for 1 hour. The organic layer was diluted with a little benzene, wasseparated and washed with water, and the product was isolated as theresidue after evaporating the solvent oil? under vacuum.

. Yield: 43 g. dark liquid. Viscosity at 21 C.: 450 poises.

Epoxy value 202 eq./kg.

8 Example 5 N,N-methylphenylethanolamine (100.7 g.) and epichlorohydrin(185 g.) were reacted in the presence of sodium hydroxide (40 g.) in amanner similar to that set out in Example 1. The product. was amobile-red-brown liquid. Yield: 100 g. (72.5%). eq./kg.

Example 6 20 parts by weight of the product of Example 5 were mixed with100 parts by weight Resin A. This mixture had a viscosity of 59 poisesat 21 C. 100 parts by weight.

of the mixture were stirred with 11 parts by weight triethylenetetramine. This composition gelled in 1 hour at 40 C. and after afurther 2 hours at 100 C. had cured to form a hard, tough resin whichhad a heat deflection temperature of 75 C. and a flexural strength of1420 kg./sq. cm.

Example 7 N-phenyl-di-Z-proponolamine (104.5 g.) and epichlorohydrin(277 g.) were reacted inthe presence of sodium hydroxide (60 g.) in amanner similar to that set out in Example 1. The product was a mobileamber liquid. Yield: 138 g. (86%). Epoxy value 4.07 eq./kg.

Example 8 N-m-tolyldiethanolamine (52 g.) and epichlorohydrin (.148 g.)were eracted in the presence of sodium hydroxide (32 g.) in a mannersimilar to that set out in Example 1. The product. was an amber liquid.Yield: 66 g. (81%). Epoxy value 4.60 eq./kg. Viscosity at 21 C.: 10poises.

Example 9 Example 10 100 parts by weight of the product of Example 8were 7 warmed with 71 parts by weight hexahydrophthalic anhydride untilhomogeneous. This composition gelled in 1 hour at C. and after a further8 hours at 120 C. had cured to form a hard, tough resin, which had aheat deflection temperature of 64 C. and a flexural strength of 1054kg./sq. cm.

Example 11 N-o-tolyldiethanolamine (27.5 g.) and epchlorohydrin (80 g.)were reacted in the presence of sodium hydroxide (16 g.) in a mannersimilar to that set out in Example 1. The product was a red-brownliquid. Yield: 38 g. (88%). Epoxy value: 4.83 eq./kg.

Example 12 30 parts by weight of the product of Example 11 were mixedwith parts by weight of Resin A. This mixture had a viscosity at 21 C.of 60 poises. weight ofthis mixture with 11 parts by weight triethylenetetramine gelled in 1 hour at 40 C. and after a further 2 hours at 100C. had cured to form a hard, brittle resinwhich had a heat deflectiontemperature of 36 C. and a flexural strength of 555 kg./sq. cm.

Example 13 100 parts by weight of the product of Example 11 were warmedwith 74 parts by weight hexahydrophthalic anhydride until homogeneous.This composition gelled in 2 hours at 80 C. and after a further 8 hoursat C. had cured to form a hard resin which had a heat deflectiontemperature of 59 C. and a flexural strength of 927 kg./sq. cm.

Epoxy value: 3.02

100 parts by Example 14 Bis-(p-diethanolanilino)ketone (50 g.) andepichlorohydrin (120 ml.) were stirred and heated under reflux, theapparatus being fitted with a water entrainer of the Dean and Starktype. Sodium hydroxide g.) in aqueous Z-methoxy-ethanol was addedportionwise over 3 hours. After a further 15 mins. no more waterseparated out on the water entra-iner and diatomaceous earth g.) wasadded and the cooled mixture filtered. Excess epichlorohydrin wasdistilled ofr at 14 mm. pressure (maximum pot temperature 120 C.), theresidue taken up in trichloroethylene (250 ml.) and washed with hotwater (5x250 ml.) and the solution evaporated at 0.2 mm. (maximum pottemperature 140 C.). The residual bright yellow stilt resin had an epoxycontent of 4.4 equivalents per kilo and a low chlorohydrin content(0.042 equivalent per kilo).

Example 15 10 parts by weight of the resin of Example 14 were mixed with2.2 parts by weight of 4,4-diamino-diphenylmethane. The mixture gelledwithin 10 mins. at 140 C. and after a further 16 hours at 140 C. hadcured to form a tough, infusible insoluble resin which had a heatdeflection temperature of 118 C.

Example 16 (a) 19.4 parts by weight of the resin of Example 1 and 11.4parts by Weight of bis-(4-hydroxyphenyl)dimethylmethane were mixed andheated to 160 C. and the reaction was followed by determination of theepoxy content of the mix. In 2 hours the epoxy value fell from aninitial value of 2.67 to an epoxy of 0.50 yielding a brittle solid.

(b) Repetition of the above fusion process in the presence of 0.002 partby weight of lithium chloride gave a final epoxy content of 0.48 after30 mins. and yielded a brittle resin.

Example 17 70 parts by weight of the resin of Example 1 and 30 parts byweight of a butylated melamine formaldehyde resin (Cibamin N86) and 2parts by weight of phthalic anyhdride were dissolved in a mixture ofxylene and nbutanol and applied to an aluminium panel and the panelstored for 30 mins. at 150 C. when a flexible and acetone-insoluble filmwas formed.

Example 18 10 parts by weight of the resin of Example 18 Were mixed with7.5 parts by Weight of methyl nadic anhydride. The mixture gelled at 20C. within 48 hours to give a brittle solid and the mixture could becured at 140 C. for 24 hours to a tough resin with a heat deflectiontemperature of 105 C.

Example 21 Methylene-bis-(p-diethanolaniline) (31.5 g.) andepichlorohydrin (110 ml.) were reacted with sodium hydroxide (20 g.) andthe product worked up as described in Example 14, affording a lightyellow viscous oil with an epoxy content of 4.8 equivalents per kilo.

1 0 Example 22 10 parts by weight of the resin of Example 21 and 2.4parts by weight of 4,4diaminodiphenylmethane were mixed and heated to140 C. The mixture gelled within 10 mins. and cured within 16 hours to atough resin with a heat deflection temperature of 109 C.

Example 23 10 parts by weight of the resin of Example 21 and 7.5 partsby weight of methyl nadic anhydride when mixed elled within 48 hours at20 C. and could be cured at 140 C. for 24 hours to a tough resin with aheat deflection temperature of 98 C.

Example 24 Isopropylidene-bis(p-diethanolaniline) (35 g.) andepichlorohydrin (100 ml.) were reacted with sodium hydroxide and theproduct isolated as described in Example 14, giving a light brown stiffres-in with an epoxy content of 4.6 equivalents per kilo.

Example 25 10 parts by weight of the resin of Example 24 and 2.2 partsby weight of 4,4'-diaminodiphenyhnethane were mixed and the mixtureheated at C. Gelation occured Within 10 mins. and after 16 hours themixture had cured to a tough, infusible, insoluble mass with a heatdeflection temperature of 119 C.

Example 26 10 parts by weight of the resin of Example 24 and 7.5 partsby weight of methyl nadic anhydride were mixed, the mix gelled after 48hours at 20 C. to a solid product and when cured at 140 C. for 24 hoursgave a tough, infusible, insoluble resin with a heat deflectiontemperatureof 106 C.

Example 27 Methylene (p-diethanolaniline) (m-ethyl-p-diethanolaniline)(80 g.) and epichlorohydrin (200 ml.) were re.- acted with sodiumhydroxide (48 g.) and the product isolated as in Example 14. Theresidual viscous brown oil (96 g.) had an epoxy value of 4.3 equivalentsper kilo.

Example 28 Methylene 'bis-(p-N-methylethanolan'iline) (61.5) andepichl-orohydrin (200 ml.) were reacted with sodium hydroxide (24 g.)and the product isolated as in Example 14, giving a stiff brown resinwith an epoxy value of 2.0 equivalents per kilo.

Example 29 Bis-(p-diethylanolaniline)ether (69 g.) and epichlorohydrin(200 ml.) were reacted with sodium hydroxide (45 g.) and the productisolated as in Example 14 giving a brown viscous oil with an epoxy valueof 4.5 equivalents per kilo.

Example 30 1.0 parts by weight of the resin of Example 27 and 2.1 partsby weight of 4,4-diaminodiphenylmethane were mixed and the mixtureheated at C. Gelation .occurred within 10 mins. and after 28 hours themixture had cured to a tough, infusihle, insoluble mass with a heatdeflection temperature of 94 C.

Example 31 10 parts by weight of the resin of Example 27 and 1.05 partsby weight of 4,4-diaminodiphenylmethane were 1 1 mixed and the mixtureheated at 145 C. Gelation occurred within 1 hour and after 28 hours themixture had cured to an infusible, insoluble mass with a heat defiectiontemperature of 50 C.

#12 at 145 C. for 24 hours; 160 C. for 40 hours, and finally at 240 C.for 18 hours, The tough, insoluble, infusible product had a heatdeflection temperature of 231 C.

Example 41 Example 33 A mixture of N-phenyldrethanolamrne (181 g.),c0nparts by weight of theresin of Exampl 24 and centrated hydrochloricacid (115 g. 36% W./w.) and pa by wslsht xilsmmedlphfnyhnethsne wereformalin 75 ml. 40% w./w.) was kept at 98 0. for 64 mlxed f P mlxiureheated at 145 Gelatlofl hours. The product was made alkaline with 50%aque- Wlthm 10 mmmes a after 28 hours mlxt'um 10 ous caustic sodasolution, cooled to 20 C., and the aquehad cured to a tough, lnfusible,insoluble mass with a heat ous layer was dec.anted dcflectlontemperature of 150 The residual polynuclear ethanolamine was dissolvedin a l 34 epich-lorohydrin' (460 ml.) and reacted in the presence ofcaustic soda (120 g.) by the method of Example 14 af- 10 parts y Weightof theresl. of P 29 15 'fording a brown viscous resin with an epoxycontent of parts by 'we1ght of methyl nadic anhydride were mixed 4 0equivalents per kilo and the mixture gelled after 48 hours at C. to asolid product, and when cured at 145 C. for 28 hours gave a Example 42tough, infusible, insoluble mass with a heat deflection 20 parts f theresin of Example 41 were mixed with temperature of 94 20 4 parts of4,4-diaminodiphenylmethane. After heating Example 35 at 135 C. for 24hours a tough, infusible, insoluble resin 12 parts b i h f h resin fExample 19 was with a heat deflection temperature of 135 C. was obmixedwith 50 parts by weight of the Resin A of Example tained- 2 and 21.5parts by weight of phthalic anhydride. This Example 43 mixture gel-ledin 15 minutes at 120 C. and after a fur- 20 parts f the resin f Example41 were mixed with 3 9 at 0 had F to form a hard l 13.4 parts ofmethylendomethylene-tetrahydrophthalic t resin which had a heatdeflection temperature of 73 C. anhydride and heated f 24 hours at 5. C.f ll d by Exam le 36 24 hours at" 240 A tough, infusible, insolubleresin Ndphenyldiethanolamine g 025 and 3O giigheda heat deflectiontemperature of 143 C. was obepoxybutyl chloride (80 g., 0.75 mol) werereacted with a Example 44 total of 19 g. of solid sodium hydroxide inthe manner described in Example 1, giving a pale yellow liquid (57 g.)In this example the accfilefatol' efiect of h diglyddyl 4 containing3.19 epoxy eq./kg. and 0.03 chlorohydrin ether ofN'phellyldiethanolamine (P p as described 1 eq./kg. Viscosity at 21 0.:23 poises. Example 1) on the cure of a Bisphenol A epoxideby E w l 37anhydrides is illustrated.

xamp e The Bisphenol A epoxide was that described as ResinBis-(p-diethanolanilino)sulfone .(373 parts by weight) A in Example 2and the curing time is here defined as the and epichlorohydrin (1200parts by weight) were treated time required for the mixture to becomeinfusible at the with sodium hydroxide (210 parts by weight) by the 40curing temperature. Each composition contains 1.00 anmethod of Example14. The stiff pale yellow resin had hydride equivalent per epoxideequivalent. an epoxy content of 4.7 equivalents per kilogram. Theresultsare listed in the following table:

Parts of 1 Parts of Curing Time to become Anhydride anhydride peraccelerator per temperature intusible at 100 parts 0 parts T" 0.temperature ResinA RcsinA T Pbthalic Anhydrlde--. 91.7 o 120 168 hours.

D0 96.4 5 120 7.5 hours. Do 101.0 10 120 Ghours. Hexahydrophthallc 79.30 100' 72 hours.

Anhydride.

Do 83.3 5 100 Zhours. Do 87.4 10 100 1.5 hours.

Example 38 Example The resin from Example 37 (20 parts by weight) was Inthis example the value of compounds of the present mixed with4,4-diaminodiphenylmethane (4.6 parts by invention as reactive diluentsin known epoxide anhydride weight) at 100 C, to give a clear mobileliquid. Gelasystems, is demonstrated. tion occurred after being heatedat 145 C. for 10 min- The diglycidyl ether of N-phenyldiethanolamine(preutes. After being cured at 145 C. for 24 hours the inp d asdescribed in Example s d as a reactive fusible, insoluble, tough producthad a heat deflection diluent in a hardenable Composition comprisingReSiIl A temperature f161 C 7 (prepared as described in Example 2),tris-(dimethyl- E l 39 ammomethyl) phenol as accelerator and a mixtureof anxa-mp hydrides as hardening agent. The resin from Example 37 (20parts by weight) was The composition of the hardening agent was asfollows: mixed with 4,4'-diaminodiphenylsulfone (6.5 parts by 78 partshexahydmphthalic anhydride weight) at 130 C. to give a clear mobilemelt. Gelation 13 pal-ts tetrahydrophthalic anhydride occurred after 20minutes at 145 C., and after further 9 parts phthalic anhydride heatmgat 1450 for 24 hours mfuslble, msolu' and suflicient anhydride was addedtogive 1.0 anhydride ble, tough product had a heat deflectiontemperature of equivalent per epoxide equivalent in each formulation 182C. The curable compositions were formulated as follows:

Example Composition 1: The resin from Example 37 (20 parts by weight)was 100 parts ResinA mixed with methyl nadic anhydride (15.4 parts byweight) 75.5 parts hardening agent at 20- C. to give a clear solution.The solution was cured 1 part accelerator I 3,244,73 1 13 14 Composition2: compounds of the formula 20 parts diglycidyl ether ofN-phenyldiethanolamine 100 parts Resin A 91 parts hardening agent 1 partaccelerator 5 X2 I N?H(IDHOCHiCHCHRs The properties of castings preparedby curing the com- R1 R2 n positions for 2 hours at 100 C. followed by 2hours at X3 [Y] 1 180 C. were measured according to the procedures laidX1 down and published by The American Society for Testing R1 R2Materials. The references to the test methods used are 10 l l giventogether with the results obtained in the table. X f CH CH O CH2 ET Itcan be seen that the useful decrease in viscosity of A O n the uncuredcomposition brought about by the addition of X3 A R1 R: O A R1 R2 0 l ll A R1 R2 0 NCHCHO-CHzCHCH-Rt l I I I\IICHCH0CII2CH-CHR3 X3ITICHCHO-CH2CH-CH-R3 a X1 1L J C X3 L t t X5 X3 X1 X3 q X1 X:

the glycidyl ether of N-phenyldiethanolamine is accornwhere X X X and Xeach are members selected from panied by an increase in both fiexuralstrength and moduthe class consisting of hydrogen atom and lower alkyllus of elasticity of the castings and that the concomitant of 1 to 4carbon atoms, R R and R each are selected decrease in heat deflectiontemperature is small. from the class consisting of hydrogen atom andmethyl Test or property Test method Composition 1 Composition 2Viscosity of uncured composition 17.4 n i 10.9 poises. Heat deflectiontemperature ASTM D648-56. 102 C- 90.5 C. Flexural strength. ASTMD790-59T. 1257 kg./sq. cm. 1313 kgJsq. cm. Modulus of elasticity byflexure ASTM DTSJO-59T. 3.335100 kgJsq. 4.935( kgJsq.

What is claimed is: group, Z is a lower alkyl group of 1 to 4 carbonatoms, 1. Glycidyl ethers selected from the group consisting Arepresents a member selected from the class consisting of compounds ofthe formula of lower alkyl group of 1 to 4 carbon atoms and radical ofthe formula -CHOHOHzCH--CHR R1 R2 R1 R2 0 I Y is a member selected fromthe class consisting of Z-ITICHOHOCHzCH/-CHR 0 a O o-, oand 3- X1 X4 g ilit a and b each are selected from the class consisting of X5 X3hydrogen atom and lower alkyl group of 1 to 4 carbon atoms, n and prepresent integers of at least 1 and at most 2, and q is an integer ofat least 1.

2. The digly-cidyl ether of N-phenyl-diethanolamine. compounds of theformula 3. The monogylcidylet'her of N-methyl-N-phenyl-ethanolamine.

4. The diglycidylether of N-phenyl-di-Q-propanolamine. 5. Thediglycidylether of N-(m-tolyl)-diethanolamine. X1 6. The diglycidyletheror N-(o-tolyl)-diethanolamine.

7. The tetraglycidylether of bis-(p-diethanol-anilino) xil-N-oH-oiat-o-orn-oH--0HR3 k t ne.

I! R] R2 7 8. The tetraglycidyl ether or methylene-bis (p-di X3 Xethanol-aniline) 9. The diglyciclyl ether ofmethylene-bis-(p-N-methylethanol-aniline) 10. The tetraglycidyl ether ofbis(p-diethanol-aniline) d fth formula ether compw S 6 11. Thetetraglycidyl ether of bis(p-diethanol-anilino) sulfone.

12. The tetraglycidyl ether of isopropylidene-bis(p-di- Xl lethanolaniline).

oH-oH-o orno11---o11n 13. The tetraglycidyl ether ofN,N,N,N-tetraethanol- X benzidine.

| 14. The di(2,3-epoxybutyl)ether of N-phenyl-dietha- (I3H |3I-IoCH2Orr/oHR j melamine X1 R1 R2 0 n (References on following page) 15 16References Citefl by the Examiner Paquin, Epoxydverbindungen undEpoxydharze, Sprin- NITED TATE PATENTS ger'verlag- U S S Republic ofSouth Africa Patent Journal, vol. 2, No. 59, r Orthner Ct a1 P g2,143,388 1/1939 Schlack 260348 5 3 383,232 gg fi T1 u WILLIAM H. SHORT,Primary Examiner.

1c ey e a 3,051,664 8/1962 Turner 260-348 NICHOLAS RIZZO, Exammer- P. S.Assistant Examir1ers.'

Chemical Abstracts, 43, 7697 g-h (1949). 10

1. GLYCIDYL ETHERS SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS OFTHE FORMULA